US10246407B2 - Process for preparing biphenylamines from anilides by ruthenium catalysis - Google Patents

Process for preparing biphenylamines from anilides by ruthenium catalysis Download PDF

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US10246407B2
US10246407B2 US15/305,865 US201515305865A US10246407B2 US 10246407 B2 US10246407 B2 US 10246407B2 US 201515305865 A US201515305865 A US 201515305865A US 10246407 B2 US10246407 B2 US 10246407B2
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US20170044094A1 (en
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Thomas Himmler
Lars Rodefeld
Jonathan Hubrich
Lutz Ackermann
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Bayer CropScience AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/22—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/22—Separation; Purification; Stabilisation; Use of additives
    • C07C231/24—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C233/04—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C233/07—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/12—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups
    • C07C233/15—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/16—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
    • C07C233/24—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
    • C07C233/25—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/16—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
    • C07C233/24—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
    • C07C233/29—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring having the carbon atom of the carboxamide group bound to an acyclic carbon atom of a carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/66—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/67—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
    • C07C233/75—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring

Definitions

  • the present invention relates to a novel process for preparing substituted biphenylamides and, in a further optional stage, biphenylamines.
  • Biaryl compounds especially biphenyl compounds, are of industrial significance as fine chemicals, intermediates for pharmaceuticals, optical brighteners and agrochemicals.
  • a method possible in principle for preparation of biaryl compounds in transition metal-catalysed cross-coupling is that of double C—H activation (see, for example, S. L. Buchwald et al, Org. Lett. 2008, 10(11), 2207-10; F. Glorius et al., Angew. Chem. Int. Ed. 2012, 51, 2247-51; WO 2014/019995).
  • these methods dispense with the synthesis of a boronic acid, for example, as a starting compound, they have serious disadvantages. For instance, costly palladium or rhodium complexes are typically used as catalysts.
  • the generally low reactivity of C—H bonds frequently leads to selectivity problems (functionalization of one C—H bond in the presence of other C—H bonds).
  • biphenyl derivatives can be prepared from phenylboronic acids and phenyl halides by a Suzuki or Stille coupling, i.e. by a palladium-catalysed reaction (cf., for example, WO 01/42223, WO 03/070705, WO 07/138089, WO 09/003650, WO 09/135598).
  • biphenyl derivatives are obtained by reacting arylzinc halides with aryl halides (Bull. Korean Chem. Soc. 2000, 21, 165-166).
  • biphenyl derivatives are obtained by reacting acetanilides with aromatic boronic acids in the presence of palladium catalysts, copper(II) triflate (Cu(OTf) 2 ) and silver oxide (Ag 2 O) (Z. Shi et al., Angew. Chem. Int. Ed. 46 (2007) 5554-8).
  • palladium catalysts copper(II) triflate (Cu(OTf) 2 ) and silver oxide (Ag 2 O)
  • biphenyl derivatives are obtained by reacting arylurea compounds with aromatic boronic acids in the presence of palladium catalysts and benzoquinone (B. H. Lipshutz et al., J. Amer. Chem. Soc. 132 (2010) 4978-9). Again, the high costs of the palladium catalyst are disadvantageous.
  • biphenyl derivatives are obtained by reacting acetanilides with aromatic boronic acids in the presence of ruthenium(II) complexes, silver hexafluoroantimonate (AgSbF 6 ), Cu(OTf) 2 and Ag 2 O (R. K Chinnagolla and M. Jeganmohan, Chemical Communication, January 2014, accepted for publication).
  • the problem addressed by the present invention was thus that of providing a novel process through which biphenylamines can be obtained with a high overall yield and high purity without the use of costly palladium catalysts and under the industrially preferred reaction conditions, especially with industrially preferred solvents.
  • the present invention accordingly provides a process for preparing biphenylamides of the general formula (V) and subsequently, in an optional second stage, biphenylamines of the general formula (I)
  • Cu and Fe are each in their highest oxidation states, while all other metals except for the alkali metals are preferably in the +II oxidation state.
  • the protecting group on the nitrogen is removed in the second stage.
  • C 1 -C 4 -Alkyl encompasses methyl, ethyl, propyl and isopropyl, butyl, isobutyl and tert-butyl and is more preferably methyl.
  • C 1 -C 4 -Alkoxy encompasses methoxy, ethoxy, propoxy, isopropoxy and butoxy and is more preferably methoxy.
  • the catalyst system consists of a ruthenium catalyst, an activator, an oxidizing agent and a metal sulphate, where the metal is preferably selected from the group comprising Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II) Mg(II), Ca(II) and Al(III), further preferably from the group comprising Fe(II) and Cu(II), and more preferably Cu(II).
  • the activator of the catalyst system is selected from the group comprising Cu(I) oxide and Cu(II) oxide.
  • organoboron compounds of the formula (III) are known in principle and can be prepared by known methods.
  • one of the X 1 , X 2 and X 3 substituents is hydrogen, but it is particularly preferable that adjacent substituents are not both hydrogen.
  • Preferred embodiments of compounds of the formula (V) in the context of the present invention are (the numbers for R 1 each indicate the position):
  • the anilides of the formula (II) for use as starting materials in the first stage in the performance of the process according to the invention are known or can be obtained by known methods.
  • the first stage of the process according to the invention is performed in the presence of a ruthenium catalyst.
  • Preference is given to using [ ⁇ RuCl 2 (p-cymene) ⁇ 2 ].
  • the amount of ruthenium catalyst can be varied within wide limits. Typically, amounts of 0.1 to 20 mole percent of the corresponding complex are used. Preferably, 1 to 10 mole percent of the corresponding complex is used.
  • the first stage of the process according to the invention is performed in the presence of an activator which generates the actually active catalyst from the ruthenium complex used.
  • activators used are typically AgSbF 6 , KPF 6 , NaPF 6 , AgF, AgBF 4 . Preference is given to using AgSbF 6 , AgBF 4 and KPF 6 , particular preference to using AgSbF 6 .
  • the activator is used in amounts of 1 to 4 molar equivalents, based on the ruthenium complex. Preference is given to using 1.5 to 3 equivalents.
  • the first stage of the process according to the invention is performed in the presence of at least one oxidizing agent, the oxidizing agent used preferably being Ag 2 O.
  • the oxidizing agent is used in amounts of 0.5 to 2 molar equivalents, based on the anilide of the formula (II). Preference is given to using 1 to 2 equivalents.
  • the first stage of the process according to the invention is performed in the presence of a metal triflate or in the presence of copper(II) sulphate or copper(I) or copper(II) oxide.
  • Metal triflates used are compounds such as copper(II) triflate, manganese(II) triflate, cobalt(II) triflate, nickel(II) triflate, zinc(II) triflate, iron(II) triflate, iron(III) triflate, lithium triflate, sodium triflate, potassium triflate, magnesium triflate or calcium triflate, for example.
  • the metal triflate (or metal sulphate or copper(I) or copper(II) oxide) is used in amounts of 1 to 4 molar equivalents, based on the ruthenium complex. Preference is given to using 1.5 to 3 equivalents.
  • the first stage of the process according to the invention is performed in solvents or solvent mixtures selected from the group comprising N,N-dialkylalkanamides, for example N-methylpyrrolidone (NMP), dimethylformamide (DMF) and dimethylacetamide (DMA), dimethoxyethane (DME), methanol, ethyl acetate and water, and mixtures of these solvents.
  • NMP N-methylpyrrolidone
  • DMF dimethylformamide
  • DMA dimethylacetamide
  • DME dimethoxyethane
  • methanol ethyl acetate and water, and mixtures of these solvents.
  • Preferred solvents or solvent mixtures are those selected from the group comprising N,N-dialkylalkanamides, and further preferably among these N-methylpyrrolidone (NMP), dimethylformamide (DMF) and dimethylacetamide (DMA), and more preferably DMF, most preferably dried DMF (storage over 4 angstrom molecular sieve).
  • NMP N-methylpyrrolidone
  • DMF dimethylformamide
  • DMA dimethylacetamide
  • DMF dimethylacetamide
  • water is a preferred solvent, which surprisingly gave the product in a relatively good yield.
  • the first stage of the process according to the invention is generally performed at temperatures in the range from 20° C. to 200° C., preferably in the range from 50° C. to 150° C.
  • organoboron compound of the formula (III) is used for 1 mol of anilide of the formula (II).
  • the second stage of the process according to the invention i.e. the elimination of the [—C( ⁇ O)R 2 ] protecting group on the nitrogen, can be effected under either basic or acidic conditions by known methods (cf., for example, T.W. Greene, P.G.M. Wuts, Protective Groups in Organic Synthesis, Ed. 3, New York, Wiley & Sons, 1999).
  • the solvent is an N,N-dialkylalkanamide and the triflate is selected from the group comprising iron(III) triflate and nickel(II) triflate, more preferably iron(III) triflate.
  • the catalyst is [ ⁇ RuCl 2 (p-cymene) ⁇ 2 ].
  • the activator is AgSbF 6 and the oxidizing agent is Ag 2 O.
  • the biphenylamines of the formula (I) are valuable intermediates for preparation of active fungicidal ingredients (cf. WO 03/070705).
  • N-(p-tolyl)acetamide (149 mg, 1.0 mmol), [ ⁇ RuCl 2 (p-cymene) ⁇ 2 ] (30.6 mg, 5.0 mol %), AgSbF 6 (68.7 mg, 0.2 mmol), Ag 2 O (232 mg, 1.0 mmol), Cu(OTf) 2 (72.3 mg, 0.2 mmol) and phenylboronic acid (183 mg, 1.5 mmol) in dry DMF (3.0 ml) was stirred in a nitrogen atmosphere at 110° C. for 20 h. The reaction mixture was then diluted at room temperature with EtOAc (75 ml) and filtered through Celite and silica gel, and the filtrate was concentrated.
  • N-(4-fluorophenyl)acetamide (153 mg, 1.0 mmol), [ ⁇ RuCl 2 (p-cymene) ⁇ 2 ] (30.6 mg, 5.0 mol %), AgSbF 6 (68.7 mg, 0.2 mmol), Ag 2 O (232 mg, 1.0 mmol), Cu(OTf) 2 (72.3 mg, 0.2 mmol) and 3,4-dichlorophenylboronic acid (286 mg, 1.5 mmol) in dry DMF (3.0 ml) was stirred in a nitrogen atmosphere at 110° C. for 20 h. The reaction mixture was then diluted at room temperature with EtOAc (75 ml) and filtered through Celite and silica gel, and the filtrate was concentrated.

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US15/305,865 2014-04-25 2015-04-22 Process for preparing biphenylamines from anilides by ruthenium catalysis Expired - Fee Related US10246407B2 (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
EP14166058.9 2014-04-25
EP14166058 2014-04-25
EP14166058 2014-04-25
EP14189192.9A EP3009420A1 (de) 2014-10-16 2014-10-16 Verfahren zum Herstellen von Biphenylaminen aus Aniliden durch Rutheniumkatalyse
EP14189192 2014-10-16
EP14189192.9 2014-10-16
PCT/EP2015/058636 WO2015162144A1 (de) 2014-04-25 2015-04-22 Verfahren zum herstellen von biphenylaminen aus aniliden durch rutheniumkatalyse

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EP (1) EP3134383B1 (zh)
JP (1) JP6588924B2 (zh)
KR (1) KR20160148589A (zh)
CN (1) CN106232573B (zh)
BR (1) BR112016024801B1 (zh)
DK (1) DK3134383T3 (zh)
ES (1) ES2799722T3 (zh)
IL (1) IL248336B (zh)
MX (1) MX2016013879A (zh)
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EP3015452A1 (de) 2014-11-03 2016-05-04 Bayer CropScience AG Verfahren zum Herstellen von Biphenylaminen aus Azobenzolen durch Rutheniumkatalyse

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001042223A1 (en) 1999-12-09 2001-06-14 Syngenta Participations Ag Pyrazolecarboxamide and pyrazolethioamide as fungicide
WO2003070705A1 (de) 2002-02-19 2003-08-28 Bayer Cropscience Aktiengesellschaft Disubstituierte pyrazolylcarboxanilide
WO2007138089A1 (en) 2006-06-01 2007-12-06 Basf Se Process for preparing substituted biphenyls
US20080194835A1 (en) * 2004-08-27 2008-08-14 Bayer Gropscience Ag Methods for the Manufacture of Biphenyl Amines
WO2009003650A1 (de) 2007-06-29 2009-01-08 Bayer Cropscience Ag Verfahren zur herstellung von biarylen
WO2009135598A1 (en) 2008-05-09 2009-11-12 Bayer Cropscience Ag Process for preparing substituted biphenylanilides
WO2014019995A1 (de) 2012-08-02 2014-02-06 Bayer Cropscience Ag Verfahren zum herstellen von substituierten biphenylen durch c-h-aktivierung

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AR064416A1 (es) * 2006-12-21 2009-04-01 Cancer Rec Tech Ltd Derivados de purina, piridina y pirimidina condensadas con heterociclos, moduladores de pka y/o pkb, composiciones farmaceuticas que los contienen, y usos para el tratamiento de enfermedades hiperproliferativas.
KR20120061061A (ko) * 2009-04-30 2012-06-12 데이진 화-마 가부시키가이샤 4 급 암모늄염 화합물
JP2012107008A (ja) * 2010-10-29 2012-06-07 Teijin Pharma Ltd 四級アンモニウム塩化合物

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001042223A1 (en) 1999-12-09 2001-06-14 Syngenta Participations Ag Pyrazolecarboxamide and pyrazolethioamide as fungicide
WO2003070705A1 (de) 2002-02-19 2003-08-28 Bayer Cropscience Aktiengesellschaft Disubstituierte pyrazolylcarboxanilide
US20060116414A1 (en) 2002-02-19 2006-06-01 Ralf Dunkel Disubstituted pyrazolyl carboxanilides
US20080015244A1 (en) 2002-02-19 2008-01-17 Ralf Dunkel Disubstituted pyrazolyl carboxanilides
US20080194835A1 (en) * 2004-08-27 2008-08-14 Bayer Gropscience Ag Methods for the Manufacture of Biphenyl Amines
WO2007138089A1 (en) 2006-06-01 2007-12-06 Basf Se Process for preparing substituted biphenyls
WO2009003650A1 (de) 2007-06-29 2009-01-08 Bayer Cropscience Ag Verfahren zur herstellung von biarylen
US20100185015A1 (en) 2007-06-29 2010-07-22 Bayer Cropscience Ag Process for preparing biaryls
WO2009135598A1 (en) 2008-05-09 2009-11-12 Bayer Cropscience Ag Process for preparing substituted biphenylanilides
EP2119697A1 (en) 2008-05-09 2009-11-18 Bayer CropScience AG Process for preparing substituted biphenylanilides
US20110092736A1 (en) 2008-05-09 2011-04-21 Bayer Cropscience Ag Process for Preparing Substituted Biphenylanilides
US8455689B2 (en) 2008-05-09 2013-06-04 Bayer Cropscience Ag Process for preparing substituted biphenylanilides
WO2014019995A1 (de) 2012-08-02 2014-02-06 Bayer Cropscience Ag Verfahren zum herstellen von substituierten biphenylen durch c-h-aktivierung
US20150203440A1 (en) 2012-08-02 2015-07-23 Bayer Cropscience Ag Process for preparing substituted biphenyls by c-h activation

Non-Patent Citations (10)

* Cited by examiner, † Cited by third party
Title
Brasche et al. "Twofold C-H Functionalization: Palladium-Catalyzed Ortho Arylation of Anilides", Organic Letters, (2008) vol. 10, No. 11, pp. 2207-2210.
Brasche et al. "Twofold C—H Functionalization: Palladium-Catalyzed Ortho Arylation of Anilides", Organic Letters, (2008) vol. 10, No. 11, pp. 2207-2210.
Chinnagolla ("Ruthenium-catalyzed ortho-arylation of acetanilides with aromatic boronic acids: an easy route to prepare phenanthridines and carbazoles" Chem. Commun. 2014, 50, 2442-2444, first publicly available on Jan. 7, 2014, and including SI, p. 1-59). *
Fuerstner et al. "What is Amphidinolide V? Report on a Likely Conquest", Chem, Int. Ed. vol. 46 (2007), pp. 5554-5558.
Jeganmohan ("Regioselective ortho-arylation and alkenylation of N-alkyl benzamides with boronic acids via ruthenium-catalyzed C-H bond activation: an easy route to fluorenones synthesis" Org. Lett., 2012, p. 5246-5249). *
Jeganmohan ("Regioselective ortho-arylation and alkenylation of N-alkyl benzamides with boronic acids via ruthenium-catalyzed C—H bond activation: an easy route to fluorenones synthesis" Org. Lett., 2012, p. 5246-5249). *
Jeong et al. "A Facile Preparation of the Fluoroaryl Zinc Halides: an Application to the Synthesis of Diflunisal", Bull. Korean Chem. Soc. (2000), vol. 21, No. 2, pp. 165-166.
Nishikata et al "Cationic Palladium(II) Catalysis: C-H Activation/Suzuki-Miyaura Couplings at Room Temperature", J. Amer. Chem. Soc., vol. 132 (2010), pp. 4978-4979.
Nishikata et al "Cationic Palladium(II) Catalysis: C—H Activation/Suzuki-Miyaura Couplings at Room Temperature", J. Amer. Chem. Soc., vol. 132 (2010), pp. 4978-4979.
Wencel-Delord et al. "[RhIIICp*]-Catalyzed Dehydrogenative ArylAryl Bond Formation", Angew. Chem. Inst. Ed. (2012) vol. 51, pp. 2247-2251.

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